Journal of Petroleum Science and Engineering 48 (2005) 169 – 184

www.elsevier.com/locate/petrol

Viscosity of water-in-oil emulsions: Variation with

temperature and water volume fraction
Marco A. Farah a, Roberto C. Oliveira b, Jorge Navaes Caldas a,
Krishnaswamy Rajagopal c,*
a
Petroleo Brasileiro S.A., Rua General Canabarro, 500, Maracanã, Rio, CEP 2057-900, Brazil
b
Petroleo Brasileiro S.A., Cenpes, Cidade Universitária, Brazil
c
LATCA–Laboratório de Termodinâmica e Cinética Aplicada–Escola de Quı́mica, Departamento de Engenharia Quı́mica,
Universidade Federal do Rio de Janeiro, UFRJ, Cidade Universitária, C.P. 68452, CEP 21949-900, Rio de Janeiro, Brazil
Received 28 October 2004; received in revised form 7 June 2005; accepted 25 June 2005

Abstract

Water-in-oil emulsions are important in the petroleum industry in production operations, where the water content of the
emulsion can be as high as 60% in volume, also in petroleum refining operations where generally the water content is low. The
effective viscosity of water-in-oil emulsions depends mainly on the volume fraction of dispersed phase and temperature, along
with several minor effects, such as shear rate, average droplet size, droplet size distribution, viscosity and density of oil. Using
six different crude oils, the effective viscosities of several synthetic water-in-oil emulsions are measured at atmospheric pressure
using a dynamic viscosimeter for different shear rates, temperatures and volume fractions of the dispersed phase. The ASTM
equation, method D-341, for describing viscosity as a function of temperature is extended to include the variation of dispersed
phase volume fraction. The proposed equation gives good correlation between the measured viscosities of water-in-oil
emulsions as a function of temperature and the volume fraction of water.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Viscosity; Rheology; Water-in-oil emulsions; Data correlation

1. Introduction crude oil production and the water content can be as

Water-in-oil (W/O) emulsions are very common in
the petroleum industry. They form naturally during
* Corresponding author. Tel.: +55 21 2562 7654; fax: +55 21
2562 7567.
E-mail address: raja@eq.ufrj.br (K. Rajagopal).
0920-4105/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.petrol.2005.06.014
high as 60% in volume. The W/O emulsions can also
form accidentally during the refining operations, sto-
rage and distribution. In these cases, the water content
rarely attains high percentage values. Sometimes, the
water is added to oil phase on purpose in order to
produce stable W/O emulsions of fuel oils with
improved combustion characteristics.
170 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184
In general, these W/O emulsions form sponta-
neously due to the presence of natural surfactants
existing in the oil phase and are stable. It is known
that the viscosity of a W/O emulsions is strongly
augmented by increasing its water volume ratio and
by decreasing the temperature (Krieger and Dough-
erty, 1959). There are several correlations between the
relative viscosity (l r) of the W/O emulsions and their
water volume content and oil phase density (Pal,
1998, 2001). Very few experimental data are available
in the literature and there is only one correlation for
describing the variation of the viscosity of water-in-oil
emulsions with temperature and volume fractions
(Ronningsen, 1995).
With the objective of evaluating correlations of the
viscosity with the temperature and volume fraction of
dispersed phase, the effective viscosities of several
synthetic W/O emulsions are measured using different
crude oils, varying shear rate, temperature and volume
fraction of dispersed phase. From this data, the rheo-
logical behavior of water-in-oil emulsions can be
studied.
The main objective of this study is to present a
method to estimate accurately the variation of
kinematic viscosity of W/O emulsions with tem-
perature and water volume fraction. The models
for suspension viscosity as a function of tempera-
ture and dispersed phase concentration are
described in Section 2. The present experimental
procedure is described in Section 3. The proposed
correlation is compared with literature correlations in
Section 4. The conclusions from this study are given in
Section 5.
2. The models for emulsion viscosity
The viscosity (l) of mono-disperse water–oil
emulsions with similar densities of phases and with
low interfacial tension is usually a function of the
following variables: temperature (T), volume fraction
of dispersed phase (V), viscosity of the continuous
phase (l C), viscosity of the dispersed phase (l D),
shear rate (ċ), droplet radius (r), and pressure ( P).
In a given crude oil at constant pressure, the principal
variables involved in the viscosity of a water emulsion
are the temperature and the concentration of the dis-
persed phase.
2.1. Models at constant temperature
Most of the existing models estimate the relative
viscosity of the emulsion (l r), defined as the ratio
between the viscosities of the emulsion (l) to that of
the continuous phase(l C):
l
lr ¼ : ð1Þ
lC
Einstein (1906, 1911) developed a thermodynamic
model for colloids and proposed that the relative
viscosity (l r) of emulsion increases linearly with the
volume fraction of dispersed phase (V):
lr ¼ 1 þ 2:5V : ð2Þ
Taylor (1932) considered the influence of the visc-
osities of both the dispersed and continuous phase and
proposed an expression valid for emulsions with small
concentration of dispersed spherical drops:
  
ðk þ 0:4Þ
lr ¼ 1 þ 2:5 V ð3Þ
ð k þ 1Þ
where k, is defined as the ratio of the viscosity of the
dispersed phase (l D) to that of the continuous phase
(l C):
lD
k¼ : ð4Þ
lC
For dispersions of spherical solid particles, the
ratio of the viscosity of dispersed phase to that of
continuous phase k, tends to infinity. In this case, Eq.
(3) becomes Einstein’s model, Eq. (2).
At high concentrations of dispersed phases the
droplets can interact and deform from the original
spherical shape. Choi and Schowater (1975) and
Yaron and Gal-Or (1972) have proposed correction
factors as a function of volume fraction of dispersed
phase to take into account the deformation of droplets:
l  
lr ¼ ¼ 1 þ f V 1=3 V ð5Þ
lC
where f(V 1/3) is calculated in two different equations
given in the references.
Phan-Thien and Pham (1997) have developed
another model for concentrated emulsions using the
 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184 171

approach of effective medium averaging, valid for low where c 0, c 1 and c 2 are constants and N Re,p is the
capillary numbers (N c): Reynolds particle number given by
 3=5    
2=5 2lr þ 5k 1 qc ċr2
lr ¼ : ð6Þ NRe; p ¼ ð11Þ
2 þ 5k 1V lc
In this model, the relative viscosity increases line-
arly with (V) at low concentrations and grows asymp- where (q c) and (l c) is the continuous phase density
totically when (V) tends to unity. and viscosity, (r) is the particle radius and (ċ) is the
Krieger and Dougherty (1959), have proposed an shear rate.
empirical model, valid for high concentrations of the Pal (2001) has recently reviewed and evaluated
dispersed phase, considering the maximum packing several theoretical viscosity models for several dilute
concentration of the dispersed phase, V m, when the and concentrated emulsions.
viscosity of suspension becomes infinite. The maxi- All these models only describe the variation of
mum packing concentration V m in turn depends on viscosity as a function of dispersed phase volume
size of the drops: fraction or the ratio between the viscosity of dispersed
  ½lVm phase and that of the continuous phase. The signifi-
V cant effect of temperature on the viscosity is not
lr ¼ 1  ð7Þ
Vm considered in any of these models.
where (V m) is the maximum concentration of dis-
persed phase and [l] the intrinsic viscosity. 2.2. Variation of viscosity of emulsions with
temperature
l
½l ¼ D  1 ð8Þ
lC
Ronningsen (1995) has proposed a correlation for
There is no simple method to measure experimen- the viscosity of W/O emulsions as a function of the
tally V m for emulsions. For estimating V m, the values dispersed phase volume fraction and the temperature:
of V vs. (l r  1) 1 can be extrapolated for a point
where the ordinate becomes zero. As the relative lnðlr Þ ¼ a1 þ a2 T þ þ a3 V þ þ a4 T V ð12Þ
viscosity of suspensions approaches infinite as V
tends to V m and this extrapolation method gives rea- where a 1, a 2, a 3 and a 4 are the coefficients of the
sonable values of V m. In the limit of low volume correlation. This correlation is based on the exponen-
fractions the equation of Krieger and Dougherty tial relationship between the viscosity and the dis-
(1959) reduces to that of Taylor: persed phase volume fraction originally suggested
by Richardson (1950) and was obtained through an
  ½lVm
V analysis of experimental data of viscosity at different
lr ¼ lim 1  temperatures and shear rates.
V Y0 Vm
   For crude oils and theirs fractions ASTM (2001)
V recommends a modified form of Walther’s model
¼ 1 ð  ½lVm Þ ¼ 1 þ ½lV : ð9Þ
Vm (1931), for the variation of the kinematic viscosity
(m) with the temperature:
Based on experimental studies and dimensional
analysis, Pal (1998) proposed an empirical viscosity lnðlnð zÞÞ ¼ A  B lnðT Þ ð13Þ
model for mono-dispersed emulsions, with similar
phase densities and with low interfacial tension. The z ¼ v þ 0:7 þ f ðvÞ and f ðvÞ ¼ eð1:471:84v0:51v Þ
2

flow is considered to be steady and the Brownian

movement of droplets is neglected: ð14Þ
 
6
If (m), kinematic viscosity, is larger than 2  10 m2/
Vm1=2 1  l1=
r
ð½lVm Þ
¼ c0 þ c1 log NRe; p s, f(m) is equal to zero where (z) is given by Eq. (14),

2 and (A) and (B) are parameters characteristic of each
þ c1 log NRe; p ð10Þ product, and (T) is absolute temperature (K).
172 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184

Eqs. (13) and (14) are the ASTM equation for the Table 2
variation of the kinematic viscosity with the tempera- Properties of the selected oils
ture widely accepted in the petroleum industry as Oil API Asphaltenes Wax Absolute *WAT(1) *WAT(2)
(% m/m) (% m/m) viscosity (8C) (8C)
method D341 of ASTM (2001). However, it has
103 (Pa s)
been used only for petroleum and their fractions. at 30 8C
1 22.3 1.7 3.4 60.4 19.0 19.0
2 18.9 1.9 b1.7 284 22.0 22.0
3. Experimental data for petroleum–water 3 24.6 b0.5 3.9 56.3 21.7 21.7
emulsions 4 28.2 0.6 4.3 24.4 17.7 17.7
5 15.7 5.9 1.7 1559 18.7 18.9
6 40.9 0.5 4.7 5.48 – 14.7
Six crude oils were selected, with density ranging
from 158 to 408 API, and of different chemical *WAT(1) = Experimental wax appearance temperature by differen-
tial scanning colorimeter.
natures from heavy aromatics to light paraffinic
*WAT(2) = Obtained by breakpoint of viscosity – temperature curve
according to their characteristics obtained through using extended ASTM D 341 equation.
the analytical methods presented in Tables 1 and 2,
using the Speight (2001) classification. The W/O
emulsions for oils of high API, 38, were more oils and their emulsions were determined using a
difficult to stabilize, specially for higher water digital Brookfield viscosimeter, model LVDIII,
volume fractions. coupled to a microcomputer, and are presented in
Synthetic emulsions, similar to those found in Table 3. Shear stress as a function of shear rates for
the petroleum fields were prepared. For this, the several temperatures at a given dispersed phase
droplet distribution and average size was determined volume fraction were measured. The temperature
and verified with natural emulsions using specific range was chosen to include the expected Wax
experiments. Synthetic emulsions with the same Appearance Temperature (WAT) of oil. WAT was
droplet distribution and average size in a homoge- determined by Differential Scanning Colorimeter
nizer equipped with digital rotation indication were (DSC) and it can be also calculated by an extension
prepared. Different W/O emulsions were prepared of ASTM method D-341. This procedure gives
with 10%, 20%, 30%, 40% and 60% of saline good results as observed in Table 2 and utilizes
water containing 50 kg of sodium chloride per viscosity measurements and the WAT value is
m3. A rotation of 10,000 rpm was used for 3 min obtained by identifying the temperature when the
and the stability of the emulsions was verified in slope viscosity–temperature curve reaches the
rest condition after 4 h and at 50 8C. Only the bbreak-pointQ.
emulsions that were clearly stable under these con- The viscosities obtained for different dispersed
ditions were considered. The viscosities of the crude phase volume fractions, temperatures and shear rates
were compared.

Table 1
Analytical methods utilized 4. Results and discussion
Property Procedure
Viscosity (Pa s) ASTM D 2893-87 4.1. Rheograms of oil and their emulsions
API density ASTM D 4052
Water in the oil (% v/v) ASTM D 4377-93 Fig. 1a–c represents rheograms, shear stress vs.
Wax content (% w/w) SMS 1769-4a shear rate, for crude oil number 1 and its W/O emul-
Asphaltene content (% w/w) PETROBRAS 1974b
Wax appearance temperature (WAT) (8C) DSCc
sions at different temperatures and dispersed phase
a volume fractions. The rheograms show that the beha-
Shell Standard Method for wax content in oil.
b
Petrobras standard method for asphaltenes content in oil by
vior of the dehydrated oil and its emulsions are influ-
precipitation in n-heptane. enced by the temperature. In Fig. 1a, the straight line
c
Differential Scanning Colorimetry. at 20 8C, is slightly superior to the WAT value for oil
 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184 173

Table 3
Viscosity of crude oil 1 and their emulsions
Dispersed phase Shear Temperature (8C)
volumetric fraction rate (s 1) 8 12 14 16 20 25 30 35 40 45 50
Absolute viscosity, 0 10 383.9 215.7 172.9 144.6 107.0 80.2 60.7 47.5 36.9 29.8 23.6
(10 3 Pa s) 20 373.5 211.4 170.2 141.5 106.1 79.5 60.4 47.1 36.8 29.5 23.5
50 360.1 205.6 166.7 137.6 105.0 78.8 60.1 46.6 36.6 29.1 23.3
80 353.5 202.7 1654.0 135.7 104.4 78.2 59.9 46.3 36.5 28.9 23.2
10 10 784.6 391.9 300.0 237.9 170.9 126.7 97.0 73.6 57.8 44.5 36.8
20 750.1 379.5 291.4 233.2 169.0 125.2 95.5 73.1 57.3 44.7 36.6
50 706.7 363.7 280.3 227.0 166.5 123.2 93.5 72.4 56.6 45.0 36.2
80 685.4 355.9 274.9 224.0 165.3 122.2 92.5 72.1 56.2 45.2 36.0
20 10 1354.6 645.2 467.8 365.9 249.4 180.3 133.7 101.6 76.9 60.6 49.4
20 1267.5 617.5 449.6 358.4 246.6 178.8 132.5 100.1 76.8 60.2 49.0
50 1160.8 582.7 426.7 348.7 242.9 176.8 130.8 98.1 76.8 59.8 48.5
80 1109.7 565.7 415.34 343.9 241.0 175.8 130.0 97.1 76.7 59.6 48.2
30 10 1921.6 1013.5 821.9 642.1 424.7 281.9 214.8 165.9 1298.0 104.9 80.7
20 1793.5 946.8 778.1 624.5 418.6 279.1 211.9 164.9 128.0 103.6 82.2
50 1637.2 865.3 723.7 601.9 410.5 275.4 209.0 163.6 126.8 102.0 84.1
80 1562.4 826.3 697.4 590.6 406.4 273.6 207.5 163.0 126.2 101.1 85.2
40 10 2690.5 1514.6 1200.9 996.4 727.2 482.6 361.2 288.5 225.4 178.8 141.4
20 2622.2 1491.7 1184.2 984.8 719.9 478.3 358.7 286.8 224.6 178.4 141.3
50 2534.6 1461.9 1162.5 969.5 710.2 472.7 355.4 284.6 223.5 177.9 141.2
80 2490.8 1446.8 1151.5 961.8 705.4 469.9 353.7 283.4 222.9 177.6 141.2

number 1, passes through the origin confirming New-
tonian behavior of the dehydrated oil.
For the W/O emulsions, Fig. 1b and c, the New-
tonian behavior occurs at temperatures higher than
the WAT at 20 8C. The WAT depends on the
volume fraction of the dispersed phase, increasing
the volume fraction of the dispersed phase increases
this temperature. For temperatures below WAT, the
dehydrated oil and their emulsions behave as Bing-
ham fluids. At higher emulsion temperatures, the
deformability limit is lower as depicted by the
intercept.
The behavior was considered to be Newtonian in
this study if the linear regression of the rheogram data
has a coefficient of correlation (R 2) greater than 0.99
and the intercept of the regressed line is less than
5  10 4 N/m2.
4.2. Variation of viscosity with the shear rate at
several temperatures and volume fraction of dispersed
phase
Fig. 2a–c shows the variation of the viscosity with
shear rate at several temperatures and fixed volume
fraction of dispersed phase. The observations
described in Section 4.1 can also be made in these
figures. For temperatures below WAT, the viscosity
varies with shear rate, indicating that the dehydrated
oil and their emulsions behave as non-Newtonian,
Bingham fluids. Fig. 2a–c shows again that the beha-
vior of the emulsion is influenced by the volume
fraction of dispersed phase. At lower temperatures,
the presence of paraffinic crystals formed provoke
Bingham plastic behavior. This is verified in Fig. 2a
which shows that the viscosity of the dehydrated oil is
practically constant with the shear rate at temperatures
above the WAT. For emulsions, Fig. 2b and c the
higher the volume fraction of dispersed phase, the
higher is the temperature where the viscosity does
not vary with the shear rate.
4.3. Variation of the kinematic viscosity with
temperature
Fig. 3a–d represents the influence of the tempera-
ture on the kinematic viscosity of the dehydrated oil 1
and its emulsions at different volume fractions for a
fixed shear rate. For temperatures above WAT, it was
174 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184

a
35000

30000
Shear Stress (105 N/m2)

25000

20000

15000

10000

5000

0
0 10 20 30 40 50 60 70 80 90
Shear Rate (s-1)

T: TEMPERATURE CELSIUS DEGREE

T=8 T=12 T=14 T=16 T=20 T=25 T=30 T=35 T=40 T=45 T=50
b
100000
95000
90000
85000
80000
75000
Shear Stress (105 N/m2)

70000
65000
60000
55000
50000
45000
40000
35000
30000
25000
20000
15000
10000
5000
0
0 10 20 30 40 50 60 70 80 90
Shear Rate (s-1)
T: TEMPERATURE CELSIUS DEGREE
T=8 T=12 T=14 T=16 T=20 T=25 T=30 T=35 T=40 T=45 T=50
c
220000
200000
180000
Shear Stress (105 N/m2)

160000
140000
120000
100000
80000
60000
40000
20000
0
0 10 20 30 40 50 60 70 80 90
Shear Rate (s-1)
T: TEMPERATURE CELSIUS DEGREE

T=8 T=12 T=14 T=16 T=20 T=25 T=30 T=35 T=40 T=45 T=50

Fig. 1. Rheogram at different temperatures for fixed volumetric fractions of dispersed phase. (a) Dehydrated oil (0%). (b) Water-in-oil emulsion
(20%). (c) Water-in-oil emulsion (40%).
 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184 175

a
1000,00

900,00
Absolute Viscosity, (10-3) Pa.s

800,00

700,00

600,00

500,00

400,00

300,00

200,00

100,00

0,00
0,00 10,00 20,00 30,00 40,00 50,00 60,00 70,00 80,00 90,00 100,00
Shear Rate (1/s)
T: TEMPERATURE CELSIUS DEGREE
T=8 T=12 T=14 T=16 T=20 T=25 T=30 T=35 T=40 T=45 T=50
b
1400,00
1300,00
1200,00
1100,00
Absolute Viscosity 10-3 Pa.s

1000,00
900,00
800,00
700,00
600,00
500,00
400,00
300,00
200,00
100,00
0,00
0,00 10,00 20,00 30,00 40,00 50,00 60,00 70,00 80,00 90,00 100,00
Shear Rate (1/s)
T: TEMPERATURE CELSIUS DEGREE
T=8 T=12 T=14 T=16 T=20 T=25 T=30 T=35 T=40 T=45 T=50
c
3000,00

2500,00
Absolute Viscosity, (10-3) Pa.s

2000,00

1500,00

1000,00

500,00

0,00
0,00 10,00 20,00 30,00 40,00 50,00 60,00 70,00 80,00 90,00 100,00
Shear Rate (1/s)
T: TEMPERATURE CELSIUS DEGREE
T=8 T=12 T=14 T=16 T=20 T=25 T=30 T=35 T=40 T=45 T=50

Fig. 2. Absolute viscosity vs. shear rate at different temperatures for fixed volumetric fractions of dispersed phase. (a) Dehydrated petroleum
(0%). (b) Water-in-oil emulsion (20%). (c) Water-in-oil emulsion (40%).
 176
a b 2,50
2,40
2,30
2,50 2,20

ln ln (v+0.7) [vv : 10 m /s]

2,40 2,10

2
2,30 2,00
ln ln (v+0.7) [vv : 10 m /s]

2,20

-6

M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184
1,90
2

2,10
2,00 1,80
-6

1,90 1,70
1,80
1,60
1,70
1,60 1,50
1,50 1,40
1,40 1,30
1,30
1,20
1,20
1,10 1,10
1,00 1,00
5,630 5,640 5,650 5,660 5,670 5,680 5,690 5,700 5,710 5,720 5,730 5,740 5,750 5,760 5,770 5,780 5,790 5,6200 5,6400 5,6600 5,6800 5,7000 5,7200 5,7400 5,7600 5,7800 5,8000
lnT [T: K] lnT [T: K]
V = DISPERSED PHASE VOLUMETRIC FRACTION V = DISPERSED PHASE VOLUMETRIC FRACTION
V=0.10 T>WAT V=0.20 T>WAT V=0.30 T>WAT V=0.40 T>WAT V=0.00 T>WAT V=0.10 T>WAT V=0.20 T>WAT V=0.30 T>WAT V=0.40 T>WAT V=0.00 T>WAT
V=0.00 T<WAT V=0.10 T<WAT V=0.20 T<WAT V=0.30 T<WAT V=0.40 T<WAT V=0.00 T<WAT V=0.10 T<WAT V=0.20 T<WAT V=0.30 T<WAT V=0.40 T<WAT

c d
2,50
2,40
2,30 2,50
2,20 2,40
2,30
2,10
v : 10 m /s]

2,20
2,00
2

2,10

v : 10 m /s)
-6

1,90

2
2,00

-6
1,80 1,90
ln ln (v+0.7) [v

1,70 1,80

ln ln (v+0.7) [v
1,60 1,70
1,50 1,60
1,50
1,40
1,40
1,30
1,30
1,20
1,20
1,10 1,10
1,00 1,00
5,6300 5,6400 5,6500 5,6600 5,6700 5,6800 5,6900 5,7000 5,7100 5,7200 5,7300 5,7400 5,7500 5,7600 5,7700 5,7800 5,7900 5,6200 5,6400 5,6600 5,6800 5,7000 5,7200 5,7400 5,7600 5,7800 5,8000
ln T [T: K]
ln T [T: K]
V = DISPERSED PHASE VOLUMETRIC FRACTION
V = DISPERSED PHASE VOLUMETRIC FRACTION
V=0.10 T>WAT V=0.20 T>WAT V=0.30 T>WAT V=0.40 T>WAT V=0.00 T>WAT
V=0.10 T>WAT V=0.20 T>WAT V=0.30 T>WAT V=0.40 T>WAT V=0.00 T>WAT V=0.10 T<WAT V=0.20 T<WAT V=0.30 T<WAT V=0.40 T<WAT V=0.00 T<WAT
V=0.00 T<WAT V=0.10 T<WAT V=0.20 T<WAT V=0.30 T<WAT V=0.40 T<WAT

Fig. 3. Kinematic viscosity vs. temperature for fixed shear rates. (a) Shear rate, 10 s 1. (b) Shear rate, 20 s 1. (c) Shear rate, 50 s 1. (d) Shear rate, 80 s 1.
 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184 177

verified that the ASTM model can be applied to the
W/O emulsions. For temperatures below WAT, this
model can also be applied with less precision using
different parameters.
Analyzing the experimental data shown in Figs.
3a–d, it can be observed that the slopes of the curves
remain constant for T N WAT, for a fixed volume
fraction of water (dispersed phase), although for
T b WAT these slopes increase slightly at a fixed
volume fraction of water. This is due to the increase
in the volume fraction of the dispersed phase (volume
fraction of water and wax) by wax precipitation.
The shear rate is not an independent variable
because the emulsions behave as plastic Bingham
fluids, the shear stress varies linearly with shear rate
above the deformability limit.
The effective viscosity of dehydrated petroleum
and its W/O emulsions was correlated as a function

a 44
42
40
38
36
34
32
30
28
26
24
A or B

22
20
18
16
14
12
10
8
6
4
2
0
0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45
Dispersed Phase Volumetric Fraction
Temperature < WAT
A B
Shear Rate: 10 (s-1)

b
26

24

22

20

18

16

14
A or B

12

10

0
0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45
Dispersed-Phase Volumetric Fraction
Temperature > WAT
-1 A B
Shear Rate: 10 (s )

Fig. 4. Parameters A and B in the viscosity ASTM equation as a function of the dispersed-phase volumetric fraction. (a) T b WAT. (b) T N WAT.
178 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184

a 8
T=8oC
7

6
Relative Viscosity

1
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1
Dispersed Phase Volumetric Fraction
Experimental Taylor Yaron Gal-Or Choi Phan Krieger

b
8
T= 25oC
7

6
Relative Viscosity

1
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9
Dispersed Phase Volumetric Fraction
Experimental Taylor Yaron Gal-Or Choi Phan Krieger

c
8
T= 50oC
7

6
Relative Viscosity

1
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9
Dispersed Phase Volumetric Fraction
Experimental Taylor Yaron Gal-Or Choi Phan Krieger

Fig. 5. Experimental vs. predicted viscosity values for oil 1 by literature models at fixed temperature. (a) T = 8 8C. (b) T = 25 8C. (c) T = 50 8C.

of temperature by the following equations estimating At constant dispersed phase volume fraction,
parameters A, B, AV, BV: T b WAT and m N 2.0  10 6 mm2/s:
At constant dispersed phase volume fraction,
T N WAT and m N 2.0  10 6 mm2/s:
lnðlnðv þ 0:7ÞÞ ¼ A  B lnðT Þ: ð15Þ lnðlnðv þ 0:7ÞÞ ¼ AV  BVlnðT Þ ð16Þ
 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184 179

4.4. Variation of viscosity with the dispersed phase
volume fraction and temperature
The values of temperature-independent para-
meters A, B, AV and BV of Eqs. (15) and (16) were
plotted against the dispersed phase volume fraction.
This plot show a near linear variation, as may be seen
in Fig. 4a and b. These linear correlation are given by
Eqs. (17)–(20):
A ¼ k1 þ k2 V
B ¼ k3 þ k4 V
AV ¼ kV1 þ kV2 V
BV ¼ kV3 þ kV4 V :
New correlations were obtained by substituting
Eqs. (17) and (18) into Eq. (15) and Eqs. (19) and
(20) into Eq. (16):
lnðlnðv þ 0:7ÞÞ ¼ k1 þ k2 V þ k3 lnðT Þ
þ k4 V lnðT Þ for T NWAT
lnðlnðv þ 0:7ÞÞ ¼ kV1 þ kV2 V þ kV3 lnðT Þ
þ kV4 V lnðT Þ for T bWAT:
The proposed Eqs. (21) and (22) can be used to
correlate the viscosity of emulsions of a petroleum at
different dispersed phase volume fractions and at
temperatures, above and below WAT.
4.5. Comparison with literature correlations
The variation of viscosity of emulsion with
dispersed phase volume using the models related
in Section 2.1 at constant temperature were eval-
uated. The values of relative viscosity calculated by
these models as a function of dispersed phase
volume fraction are shown in Fig. 5a–c. The
experimental values are also shown in the same
figures. All these models do not have any adjus-
table parameter, although many authors have used
Krieger’s model with the maximum packing frac-
tion as an adjustable parameter. None of the mod-
els (Eqs. (3) and (6) (7) (8)) were entirely satisfactory.
ð17Þ
Perhaps the size distribution of the dispersed phase
has a greater influence on the viscosity of the
ð18Þ
emulsion even for volume fractions much lower
than the maximum packing fraction. For this rea-
ð19Þ
son, it was decided to use an empirical correlation
for experimental viscosity data for different
ð20Þ
volume fractions of dispersed phase at any given
temperature.
The proposed correlation is compared with that
of Ronningsen (1995) in Table 4 and in Fig. 6a–f
for oils 1–6. The proposed method correlated the
experimental data better than the Ronningsen
expression, even when this expression is utilized
ð21Þ
separately to correlate viscosity data for tempera-
tures above and below WAT. The proposed method
also presents better R-square coefficient and mean
deviations percent values than that of Ronningsen
ð22Þ
(1995). The values of the correlation coefficients for
the proposed and Ronningsen methods are shown in
Table 5.
The experimental data of Ronningsen (1995) were
also correlated with the proposed equation. The pro-
posed equation is better than the Ronningsen as can be
verified in Fig. 7 and Table 6.
The proposed correlation has a functional term,
(k 3 + k 4V)lnT, resulting in appropriate values for k 3
and k 4 reflecting better the increase in viscosity with

Table 4
Coefficients R-square and mean deviations for oils 1–6
Method R-square: coefficients of multiple correlation Mean relative deviation percent
Oil 1 Oil 2 Oil 3 Oil 4 Oil 5 Oil 6 Oil 1 Oil 2 Oil 3 Oil 4 Oil 5 Oil 6
Proposed range: T b WAT 0.9916 0.9933 0.9983 0.9760 0.9781 0.9966 5.4 5.2 3.2 7.4 3.6 2.7
Proposed range: T N WAT 0.9957 0.9975 0.9976 0.9870 0.9869 0.9842 3.7 3.3 3.5 5.1 8.0 6.2
Ronningsen all range 0.9653 0.9797 0.9895 0.9526 0.9228 0.9590 7.5 5.4 6.9 8.0 8.7 9.9
Ronningsen range: T b WAT 0.9957 0.9876 0.9931 0.9499 0.9205 0.8943 5.0 5.8 3.6 8.5 3.9 8.1
Ronningsen range: T N WAT 0.9383 0.9926 0.9881 0.9689 0.9812 0.9848 8.1 3.5 5.9 7.0 9.2 7.7
180 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184

a
3000

Absolute Viscosity Experimental (10-3) Pa.s]

2750
2500
2250
2000
1750
1500
1250
1000
750
500
250
0
0 250 500 750 1000 1250 1500 1750 2000 2250 2500 2750 3000
Absolute Viscosity Calculated (10-3Pa.s]
Proposed Correlation at T < WAT Ronningsen Correlation Proposed Correlation at T > WAT
b
20000
Absolute Viscosity Experimental (10-3) Pa.s

18000

16000

14000

12000

10000

8000

6000

4000

2000

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000
Absolute Viscosity Calculated (103) Pa.s

Proposed Correlation at T < WAT Ronningsen Correlation Proposed Correlation at T > WAT
c
2250
Absolute Viscosity Experimental (10-3) Pa.s

2000

1750

1500

1250

1000

750

500

250

0
0 250 500 750 1000 1250 1500 1750 2000 2250
Absolute Viscosity Calculated (10-3) Pa.s

Proposed Correlation at T < WAT Ronningsen Correlation Seqüência4 Proposed Correlation at T > WAT

Fig. 6. Experimental vs. calculated viscosity values for oils 1 to 6 by the proposed and Ronningsen methods. (a) Oil 1. (b) Oil 2. (c) Oil 3. (d) Oil
4. (e) Oil 5. (f) Oil 6.
 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184 181

d
Absolute Viscosity Experimental (10-3) Pa.s 500

450

400

350

300

250

200

150

100

50

0
0 50 100 150 200 250 300 350 400 450 500
Absolute Viscosity Calculated (10-3) Pa.s
Proposed Correlation at T < WAT Ronningsen Correlation Proposed Correlation at T > WAT
e
25000
Absolute Viscosity Experimental (10-3) Pa.s

20000

15000

10000

5000

0
0 5000 10000 15000 20000 25000
-3
Absolute Viscosity Calculated, (10 ) Pa.s
Proposed Correlation T < WAT Ronningsen Correlation Proposed Correlation T > WAT
f
300
Absolute Viscosity Experimental (10-3) Pa.s

250

200

150

100

50

0
0 50 100 150 200 250 300
-3
Absolute Viscosity Calculated (10 ) Pa.s
Proposed Correlation at T < WAT Ronningsen Correlation Proposed Correlation at T > WAT

Fig. 6 (continued).
182 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184

Table 5
Parameters of correlation* for oils 1 to 6
Oil Parameters Method
number in equations Proposed T b WAT Proposed T N WAT Ronningsen’s all range Ronningsen’s T b WAT Ronningsen’s T N WAT
Oil 1 k1 40.2 24.1 0.29 0.53  0.06
k2 34.71 18.1 4.21 3.75 3.8
k3 6.8 3.96 0.01 0.03  0.0001
k4 6.26 3.31 0.01 0.06 0.02
Oil 2 k1 21.2 22.8 0.19 0.11 0.21
k2 8.08 9.88 4.95 6.02 4.21
k3 3.31 3.67 0.002 0.004  0.003
k4 1.33 1.83 0.002 0.1  0.005
Oil 3 k1 24.0 24.0 0.53 0.54  0.51
k2 9.53 16.87 6.99 7.4 6.63
k3 3.97 3.97 0.002 0.002 0.001
k4 1.87 3.16 0.02 0.05  0.01
Oil 4 k1 30.4 25.73 0.001 0.11  0.07
k2 9.4 0.78 3.65 3.89 3.36
k3 5.12 4.3 0.003 0.008  0.001
k4 1.79 0.49 0.006 0.02 0.013
Oil 5 k1 2.62 3.28 0.77 0.37 1.19
k2 0.27 0.14 6.95 13.85 4.51
k3 0.03 0.17 0.00 0.08  0.01
k4 0.17 0.38 0.04 0.48 0.02
Oil 6 k1 52.11 108.03 1.51 1.26 2.01
k2 47.60 157.09 0.65 3.23  4.40
k3 8.94 18.82 0.10 0.08  0.12
k4 8.50 27.85 0.93 0.47 1.10
*Proposed Method: ln ln(m + 0.7) = k 1 + k 2V + k 3lnT + k 4VlnT.
*Proposed Method: ln ln(m + 0.7) = kV1+ k VV
2 + k VlnT
3 + k VVlnT.
4
*Ronningsen Method: ln m r = k 1W + k 2WV + k 3WT + k 4WTV.

reduction of temperature than the Ronningsen correla-
tion term (a 3 + a 4V)T.
5. Conclusions
From an analysis of the experimental data obtained
for six oils and their emulsions at different tempera-
tures and dispersed phase volume fractions, the fol-
lowing can be concluded:
– For the emulsions, increasing the water volume
fraction increases the temperature above which
the emulsions show Newtonian behavior.
– At temperatures lower than WAT, the emulsions
present rheological behavior of a Bingham plastic
in the measurement range of shear rate, 10 s 1 to
80 s 1.
– The variation of the kinematic viscosity of the oils
with the temperature is very well represented by
the ASTM equation for temperatures above WAT.
For temperatures below WAT, this model also
appropriately represents the variation of the visc-
osity of the petroleum with the temperature.
– For W/O emulsions, the variation of the effective
kinematic viscosity with the temperature also fol-
lows the same ASTM equation, and the slope of
viscosity–temperature ASTM curve for each con-
centration is practically the same as that for the
petroleum for temperatures above WAT.
– It is possible to correlate the effective viscosity of
emulsions with the temperature and with the dis-
persed phase volume fraction.
– The available experimental data are better corre-
lated by the proposed correlation than the Ronning-
sen (1995) correlation, even when Ronningsen’s
expression is applied separately for viscosity data
to temperatures above and below the WAT.
– It is possible to determine the WAT with very good
precision, by identifying the temperature at which
 M.A. Farah et al. / Journal of Petroleum Science and Engineering 48 (2005) 169–184 183

1000

Absolute Viscosity Experimental (10-3) Pa.s

900

800

700

600

500

400

300

200

100

0
0 100 200 300 400 500 600 700 800 900 1000
Absolute Viscosity Calculated (10-3) Pa.s
Proposed Correlation at T < WAT Ronningsen Correlation Proposed Correlation at T > WAT

Fig. 7. Experimental vs. calculated viscosity values for Ronningsen data oil 4 for the proposed and Ronningsen methods.

the slope viscosity–temperature curve changes Greek Letters

abruptly (the dbreak-pointQ). lr relative viscosity
q density
List of Symbols ċ shear rate
A, B parameters in viscosity–temperature ASTM m kinematic viscosity
equation l absolute viscosity
a 1, a 2, a 3, a 4 parameters in Ronningsen equation [l] intrinsic viscosity
c 1, c 2, c 3 parameters in Pal equation s shear stress
k ratio of viscosity of the dispersed to the
continuous phase Subscripts
k 1, k 2, k 3, k 4 parameters in equation proposed C continuous phase
k 1V, k 2V, k 3V, k 4V parameters in equation proposed D dispersed phase
f(V 1/3) function presented in Eq. (6) m maximum concentration of dispersed phase
N Re,p particle Reynolds number
Nc capillary number
r droplet radius Acknowledgments
P pressure
T temperature The authors thank Zuila Nunes Luiz and Marcia
z viscosity function Khalil Oliveira for the experimental work, Dr. Ian
V volume fraction of dispersed phase Hovell in revising the manuscript and Petrobras for
WAT wax appearance temperature permission to publish this paper. The authors grate-
fully acknowledge the scholarship given by CNPq
(Bolsa de Produtividade) to K. Rajagopal. The finan-
cial support of PETROBRAS, Projeto CNPq (contract
Table 6 number 502156/2003-1), CTPETRO/FINEP and
Coefficients R-square for oil 4 data published by Ronningsen
(1995)
PADCT III/CNT is also acknowledged.
Method R-square: coefficients Mean relative
of multiple correlation deviation percent
References
Proposed range: T b WAT 0.9959 2.6
Proposed range: T N WAT 0.9981 3.6 ASTM, 2001. Annual Book of ASTM Standards, vol. 05. ASTM,
Ronningsen all range 0.9895 6.5 Philadelphia, PA. Section 05.
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